JP7101190B2 - Manufacture of aromatic catalysts in the presence of alkali metals in the cleaning process - Google Patents

Description

The present disclosure relates to a method for producing a supported catalyst, and more particularly to producing a supported aromatization catalyst containing a transition metal and a bound zeolite base using a washing step in the presence of an alkali metal.

The standard manufacturing process for many carrier aromatization catalysts typically involves forming a bound zeolite base from a binder and a zeolite, even if the zeolite is ion-exchanged prior to the formation of the bound zeolite base. good. Bonded zeolites are generally washed prior to the addition of transition metals such as platinum and halogens, thereby forming a supported aromatization catalyst.

After forming the bound zeolite base, performing an ion exchange treatment may not be desirable as it increases the cost and complexity of the overall catalyst manufacturing process. However, it may be beneficial to enrich the bound zeolite carrier with an alkali metal in order to improve the properties of the resulting supported aromatization catalyst without the need for an ion exchange process. Therefore, the present disclosure generally relates to achieving these objectives.

Methods for producing the supported catalyst are disclosed and described herein. Methods of making the carrying catalyst include: (a) providing the bound zeolite base and (b) washing the bound zeolite base with an aqueous solution containing an alkali metal to produce an alkali metal enriched zeolite carrier, (c). An alkali metal-enriched zeolite carrier is impregnated with a transition metal and a halogen to produce a supported catalyst. Typically, the alkali metal may include potassium, rubidium, cesium, or a combination thereof, and the transition metal may include platinum.

The supported catalyst produced by the methods provided herein may be used in an aromatization process for producing aromatic compounds from non-aromatic hydrocarbons. Such catalysts have an unexpected combination of improved product selectivity with a smaller catalyst surface area and a smaller catalyst pore volume compared to supported catalysts manufactured without a cleaning step utilizing alkali metals. Can have (such as benzene or toluene).

Both the above overview and the detailed description below provide examples and are for illustration purposes only. Therefore, the above overview and the following detailed description should not be construed as limiting. In addition to those described herein, features or variations may be provided. For example, certain embodiments may be intended for combinations and partial combinations of various features described in the detailed description.
In addition, each of the following [1] to [78] is one form or one aspect of the present invention.
[1]
It is a method for manufacturing a supported catalyst.
(A) Prepare a bound zeolite base;
(B) To produce an alkali metal enriched zeolite carrier by washing the bound zeolite base with an aqueous solution containing an alkali metal;
(C) A carrier catalyst is produced by impregnating an alkali metal-enriched zeolite carrier with a transition metal and a halogen.
How to include.
[2]
The method according to [1], wherein the bound zeolite base comprises a zeolite and a binder.
[3]
The method according to [2], wherein the bound zeolite base contains from about 3% by weight to about 35% by weight of the binder based on the total weight of the supported catalyst.
[4]
The method according to [2] or [3], wherein the binder comprises an inorganic solid oxide, clay, or a combination thereof.
[5]
The method according to any one of [2] to [4], wherein the binder comprises alumina, silica, magnesia, bolia, titania, zirconia, a mixed oxide thereof, or a mixture thereof.
[6]
The method according to any one of [2] to [5], wherein the binder contains silica.
[7]
The method according to any one of [2] to [6], wherein the binder comprises montmorillonite, kaolin, cement, or a combination thereof.
[8]
The method according to any one of [1] to [7], wherein the bound zeolite base contains a bound L-zeolite.
[9]
The method according to any one of [1] to [7], wherein the bound zeolite base contains a bound Ba / L-zeolite.
[10]
The method according to any one of [1] to [7], wherein the bound zeolite base contains a bound K / L-zeolite.
[11]
The method according to any one of [1] to [6], wherein the bound zeolite base contains a silica-bound K / L-zeolite.
[12]
The bound zeolite base in step (a) is produced by a method comprising mixing the zeolite with a binder, extruding the mixture, drying and calcining, from [1] to [1]. 11] The method according to any one of paragraphs.
[13]
The bound zeolite base in step (a) is produced by a method comprising mixing K / L-zeolites with silica, extruding the mixture, drying and calcining [1]. ] To the method according to any one of [6].
[14]
The method according to any one of [1] to [13], wherein the method further comprises drying and / or calcining the alkali metal enriched zeolite carrier before step (c).
[15]
The method according to any one of [1] to [14], wherein the supported catalyst contains about 0.1% by weight to about 10% by weight of the transition metal based on the total weight of the supported catalyst.
[16]
In step (c), the alkali metal enriched zeolite carrier is subjected to tetraamine platinum (II) chloride, tetraamine platinum (II) nitrate, platinum (II) acetylacetonate, platinum chloride (II), ammonium tetrachloroplatinate (II). The method according to any one of [1] to [15], which comprises mixing with a transition metal-containing compound containing platinum chloride acid, platinum (II) nitrate, or a combination thereof.
[17]
The method according to any one of [1] to [16], wherein the halogen contains chlorine and / or fluorine.
[18]
The method according to any one of [1] to [17], wherein the step (c) comprises mixing the alkali metal enriched zeolite carrier with a chlorine-containing compound and / or a fluorine-containing compound.
[19]
The method according to any one of [1] to [18], wherein the halogen contains chlorine.
[20]
19. The method of [19], wherein the carrier catalyst contains from about 0.05% to about 5% by weight chlorine based on the total weight of the carrier catalyst.
[21]
The method according to any one of [1] to [18], wherein the halogen contains fluorine.
[22]
21. The method of [21], wherein the carrier catalyst contains from about 0.05% to about 5% by weight of fluorine based on the total weight of the carrier catalyst.
[23]
The method according to any one of [1] to [22], wherein the method further comprises drying and / or calcining the supported catalyst after the step (c).
[24]
The method according to any one of [1] to [23], wherein the method further comprises a reduction step including contacting the supported catalyst with a reducing gas stream containing hydrogen after the step (c).
[25]
The method according to [24], wherein the reduction step is performed at a reduction temperature in the range of about 100 ° C to about 700 ° C.
[26]
Any one of [1] to [25], wherein the supported catalyst has a surface area smaller than the surface area of the catalyst obtained by washing the bound zeolite base with an aqueous solution containing no alkali metal under the same catalyst conditioning conditions. The method described in.
[27]
The method according to any one of [1] to [26], wherein the supported catalyst has a surface area of about 100 m ² / g to about 170 m ² / g.
[28]
The method according to any one of [1] to [27], wherein the alkali metal enriched zeolite carrier has a surface area of about 120 m ² / g to about 250 m ² / g.
[29]
Any of [1] to [28], wherein the supported catalyst has a pore volume area smaller than that of the catalyst obtained by washing the bonded zeolite base with an aqueous solution containing no alkali metal under the same catalyst conditioning conditions. The method described in item 1.
[30]
The method according to any one of [1] to [29], wherein the supported catalyst has a pore volume of about 0.015 cc / g to about 0.05 cc / g.
[31]
The method according to any one of [1] to [30], wherein the alkali metal enriched zeolite carrier has a pore volume of about 0.025 cc / g to about 0.08 cc / g.
[32]
The method according to any one of [1] to [31], wherein the transition metal contains platinum.
[33]
The method according to any one of [1] to [32], wherein the supported catalyst contains about 0.1% by weight to about 10% by weight based on the total weight of the supported catalyst.
[34]
The method according to any one of [1] to [33], wherein the carrier catalyst comprises a TEOR of about 499 ° C (930 ° F) to about 530 ° C (986 ° F) _.
[35]
The method according to any one of [1] to [34], wherein the supported catalyst is characterized by a benzene selectivity of about 0.91 to about 0.97.
[36]
The carried catalyst has greater benzene selectivity than the catalyst obtained by washing the bound zeolite base with an alkali metal-free aqueous solution under the same catalyst production and aromatization reaction conditions, [1] to [35]. The method described in any one of the above.
[37]
The method according to any one of [1] to [36], wherein the supported catalyst has a platinum dispersity of about 50% to about 70%.
[38]
[1]- The method according to any one of [37].
[39]
The alkali metal enriched zeolite carrier is based on the total weight of the alkali metal enriched zeolite carrier, and any weight percent of sodium disclosed herein, such as 0% by weight to about 0.35% by weight, 0% by weight to. Any of [1] to [38] containing about 0.3% by weight, about 0.03% by weight to about 0.35% by weight, or about 0.05% by weight to about 0.3% by weight of sodium. The method described in paragraph 1.
[40]
The method according to any one of [1] to [39], wherein the aqueous solution contains an alkali metal salt.
[41]
The method according to any one of [1] to [40], wherein the aqueous solution contains an alkali metal chloride salt.
[42]
The method according to any one of [1] to [41], wherein the washing step comprises contacting the bound zeolite base with an aqueous solution consisting essentially of an alkali metal salt and deionized water.
[43]
The method according to any one of [1] to [42], wherein the cleaning step is performed at a cleaning temperature in the range of about 20 ° C to about 95 ° C.
[44]
The method according to any one of [1] to [43], wherein the washing step comprises 2 to 8 washing cycles; and a washing cycle time in the range of about 1 minute to about 6 hours.
[45]
The method according to any one of [1] to [44], wherein the concentration of the alkali metal in the aqueous solution is about 0.01 M to about 5 M.
[46]
The method according to any one of [1] to [45], wherein the ratio of the weight of the aqueous solution to the weight of the bound zeolite base is about 0.4: 1 to about 10: 1.
[47]
The method according to any one of [1] to [46], wherein the washing step enriches the bound zeolite base with about 0.03 mol to about 1 mol of alkali metal per kg of bound zeolite base.
[48]
The method according to any one of [1] to [47], wherein the washing step enriches the bound zeolite base with about 0.03 mol to about 1 mol of alkali metal per 1 kg of alkali metal enriched zeolite carrier.
[49]
The method according to any one of [1] to [48], wherein the step (b) is the only step of utilizing an alkali metal in the method.
[50]
The method according to any one of [1] to 49], wherein the step (b) is the only step of utilizing an alkali metal salt in the method.
[51]
The method according to any one of [1] to [50], wherein the alkali metal comprises potassium, rubidium, cesium, or a combination thereof.
[52]
The method according to any one of [1] to [51], wherein the alkali metal contains potassium.
[53]
52. The method of [52], wherein the supported catalyst has a surface area in the range of about 100 m ² / g to about 170 m ² / g and a pore volume in the range of about 0.015 cc / g to about 0.05 cc / g. ..
[54]
The method according to [52] or [53].
The aqueous solution contains potassium chloride; or
The aqueous solution further comprises rubidium, cesium, or a combination thereof.
How to include.
[55]
The method according to any one of [52] to [54], wherein the concentration of potassium in the aqueous solution is in the range of about 0.1 M to about 0.45 M.
[56]
The carrier catalyst is based on the total weight of the carrier catalyst
With about 0.2% by weight to about 5% by weight of platinum;
With about 0.1% by weight to about 1.5% by weight of fluorine;
The method according to any one of [52] to [55], which comprises from about 0.1% by weight to about 1.5% by weight of chlorine.
[57]
The method according to any one of [1] to [51], wherein the alkali metal contains rubidium.
[58]
The method according to [57], wherein the concentration of rubidium in the aqueous solution is in the range of about 0.01 M to about 5 M.
[59]
[57] or [58], wherein the aqueous solution further comprises potassium, cesium, or a combination thereof.
[60]
The method according to any one of [1] to [51], wherein the alkali metal contains cesium.
[61]
The method according to [60], wherein the concentration of cesium in the aqueous solution is in the range of about 0.01 M to about 5 M.
[62]
The method according to [60] or [61].
The aqueous solution further comprises potassium, rubidium, or a combination thereof; and
The carrier catalyst contains from about 5% to about 30% by weight of binder based on the total weight of the carrier catalyst.
How to include.
[63]
The carrier catalyst is based on the total weight of the carrier catalyst
With transition metals from about 0.2% to about 5% by weight;
With about 0.2% by weight to about 3% by weight of halogen;
Contains from about 2% to about 10% by weight cesium;
The method according to any one of [60] to [62].
[64]
A supported catalyst obtained by the method according to any one of [1] to [63].
[65]
The supported catalyst according to [64], wherein the supported catalyst has a surface area smaller than the surface area of the catalyst obtained by washing the bonded zeolite base with an aqueous solution containing no alkali metal under the same catalyst production conditions.
[66]
The carrier catalyst according to [64] or [65], wherein the carrier catalyst has a surface area of about 100 m ² / g to about 170 m ² / g.
[67]
The carrier catalyst according to any one of [64] to [66], wherein the alkali metal enriched zeolite carrier has a surface area of about 120 m ² / g to about 250 m ² / g.
[68]
One of [64] to [67], wherein the supported catalyst has a pore volume smaller than that of the catalyst obtained by washing the bonded zeolite base with an aqueous solution containing no alkali metal under the same catalyst production conditions. The carrier catalyst according to.
[69]
The supported catalyst according to any one of [64] to [68], wherein the supported catalyst has a pore volume of about 0.015 cc / g to about 0.05 cc / g.
[70]
The supported catalyst according to any one of [64] to [69], wherein the alkali metal enriched zeolite carrier has a micropore volume of about 0.025 cc / g to about 0.08 cc / g.
[71]
The supported catalyst according to any one of [64] to [7] 0, wherein the transition metal is platinum.
[72]
The supported catalyst according to [71], wherein the supported catalyst has a _TEOR of about 499 ° C (930 ° F) to about 530 ° C (986 ° F) .
[73]
The supported catalyst according to [71], wherein the supported catalyst has a benzene selectivity of about 0.91 to about 0.97.
[74]
The carrying catalyst according to [71], wherein the carrying catalyst has greater benzene selectivity than the catalyst obtained by washing the bound zeolite base with an aqueous solution containing no alkali metal under the same catalyst production and aromatization reaction conditions. catalyst.
[75]
The supported catalyst according to [71], wherein the supported catalyst has about 50% to about 70% platinum dispersion.
[76]
A reforming process comprising contacting a hydrocarbon raw material with the carrying aromatization according to any one of [1] to [75] under reforming conditions in a reactor system to produce an aromatic product.
[77]
The process according to [76], wherein the hydrocarbon feedstock comprises a non-aromatic hydrocarbon.
[78]
The process according to [76], wherein the hydrocarbon feedstock comprises a C6 _- C8 _alkane and / or a cycloalkane.

Shown is a plot of the pore volume of the alkali metal enriched zeolite carrier and the pore volume of the carrier catalyst relative to the molar concentration of alkali metal in the aqueous solution used to clean the alkali metal bound zeolite bases of cesium and potassium. .. Alkali Metal Bonding of Cesium and Potassium A plot of the platinum dispersibility of the carrier catalyst with respect to the molar concentration of the alkali metal in the aqueous solution used to clean the zeolite base is shown. FIG. 3 shows a plot of benzene selectivity, toluene selectivity and end-of-experiment temperature of a cesium-enriched carrier catalyst compared to a reference catalyst for the molar concentration of cesium in the aqueous solution used to wash the bound zeolite base. FIG. 3 shows a plot of benzene selectivity, toluene selectivity, and end-of-experiment temperature of a potassium enrichment carrying catalyst compared to a reference catalyst for the molar concentration of potassium in the aqueous solution used to wash the bound zeolite base.

Definitions The following definitions are provided to more clearly define the terms used herein. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in the present disclosure but is not specifically defined herein, unless the applicable definition is inconsistent with any other disclosure or definition applicable herein, or the definition thereof. Definitions from the IUPAC Compendium of Chemical Terminology, 2nd ^Ed (1997) may be applied unless any claim to which the definition applies is obscured or impossible. To the extent that any definition or use provided by any document incorporated herein by reference conflicts with the definition or use provided herein, the definition or use provided herein. Priority is given.

In the present specification, the features of a subject are described so that a combination of different features may be assumed within a particular aspect. For each and every aspect and feature disclosed herein, all combinations that do not adversely affect the designs, compositions, processes, or methods described herein are explicit combinations. Intended with or without description. Further, unless expressly stated otherwise, any aspect or feature disclosed herein is to illustrate the design, composition, process, or method of the invention that is consistent with this disclosure. May be combined with.

In the present disclosure, compositions and methods are often described by the term "contains" various components or processes, but unless otherwise stated, compositions and methods are "essential" from various components or processes. It may be "become" or "become".

The words "a", "an", and "the" are intended to include at least one of their plurals, eg, at least one. For example, disclosure of a "transition metal" or "halogen" is meant to include one or more mixture or combination of transition metals or halogens, unless otherwise specified.

In general, the group of elements is shown using the numbering scheme shown in the interpretation of the Periodic Table of the Elements published in Chemical and Engineering News, 63 (5), 27, 1985. In some cases, a group of elements has a common name assigned to that group (such as alkali metals of Group 1 elements, transition metals of Group 3-12 elements, and halogens or halides of Group 17 elements). May be shown using.

For any particular compound or group disclosed herein, any of the names or structures presented will be any conformational isomer that may result from a particular set of substituents, unless otherwise stated. It is intended to contain positional isomers, conformers, and mixtures thereof. Unless otherwise stated, the names or structures are all enantiomers, diastereomers, and other optical isomers (if any) of either enantiomer or racemic form, as may be recognized by those skilled in the art, as well as stereoisomers. Also includes a mixture of. For example, general references to hexane include n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethyl-butane, and 2,3-dimethyl-butane; general to butyl groups. References include n-butyl group, sec-butyl group, iso-butyl group, and t-butyl group.

In one embodiment, a chemical "group" is, even if the group is not literally synthesized in this manner, depending on how the group is formally derived from the reference or "parent" compound. For example, it is described by the number of hydrogen atoms formally removed from the parent compound to form that group. These groups may be utilized as substituents or may be coordinated or bonded to metal atoms. As an example, the "alkyl group" may formally be derived by removing one hydrogen atom from the alkane. The disclosure that a substituent, ligand, or other chemical moiety may constitute a particular "group" is subject to well-known rules of chemical structure and binding when the group is used as described. Means. When a group is described as "derived by," "derived from," "formed by," or "formed by," such terms are used in a formal sense and are otherwise referred to. It is not intended to reflect any particular synthesis method or procedure unless specified or otherwise required by the context.

Various numerical ranges are disclosed herein. When any kind of range is disclosed or requested herein, unless otherwise specified, such range includes the endpoints of that range and the subranges and combinations of subranges contained therein. It is intended to individually disclose or claim each possible number that may reasonably be included. As a representative example, the present application discloses that the methods provided herein have molar concentrations of alkali metals in aqueous solutions used in particular embodiments in the range of about 0.01 M to about 0.45 M. ing. With the disclosure that the molar concentration of alkali metal in the aqueous solution is in the range of about 0.01M to about 0.45M, the intent is that the concentration is any concentration within the range, eg, about 0.01M, about 0.05M. , About 0.1M, about 0.15M, about 0.2M, about 0.25M, about 0.3M, about 0.35M, about 0.4M, or even about 0.45M. Is. Further, the molar concentration may be in the range of about 0.01M to about 0.45M (eg, the molar concentration may be in the range of about 0.01M to about 0.2M), and this is It may also include any combination within the range of about 0.01M to about 0.45M. Similarly, all other scopes disclosed herein should be construed similarly to this example.

The word "about" is an approximation that includes that the quantity, size, formulation, parameters, and other quantities and properties are inaccurate and need not be accurate, but may be larger or smaller as needed. It may be a value, meaning that it reflects tolerances, conversion factors, rounding, measurement errors, and other factors known to those of skill in the art. In general, a quantity, size, formulation, parameter, or other quantity or characteristic is "about" or "approximately", whether or not explicitly stated to be so. The term "about" also includes different quantities due to different equilibrium conditions of the composition resulting from a particular initial mixture. Whether or not it is modified by the word "about", the claims include its amount of equality. The word "about" may mean no more than 10% of the reported number, preferably no more than 5% of the reported number.

As used herein, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen atoms. If so, other identifiers may be used to indicate the presence of a particular group in the hydrocarbon (a halogenated hydrocarbon is one or more that replaces an equivalent number of hydrogen atoms in the hydrocarbon. Indicates the presence of a halogen atom, etc.).

"Aromatic compound" means a compound comprising a cyclically conjugated moiety according to Hückel's rule (4n + 2) and containing (4n + 2) pi-electrons, where n is an integer of 1-5. Aromatic compounds include "arene" (hydroaromatic compounds such as benzene, toluene, xylene) and "heteroarene" (formally one or more methines (-C =) of cyclic conjugated double chains from arene. Heteroaromatic compounds induced by the substitution of carbon atoms, trivalent or trivalent or in a manner that maintains the number of continuous pi-electrons characteristic of aromatic systems and out-of-plane pi-electrons corresponding to the Huckel rule (4n + 2). Bonding system with divalent hetero atom) is included. As disclosed herein, the term "substituted" may be used to describe an aromatic group, arene, or heteroarene, where the non-hydrogen moiety is a hydrogen atom in the compound. Is formally replaced, and is intended to be non-limiting unless otherwise specified.

As used herein, the term "alkane" means a saturated hydrocarbon compound. If so, other identifiers may be used to indicate the presence of a particular group in the alkane (halogenated alkanes are one or more halogen atoms that replace an equivalent number of hydrogen atoms in the alkane. Show existence, etc.). The term "alkyl group" is used herein according to the definition specified by IUPAC and is a monovalent group formed by removing a hydrogen atom from an alkane. The alkane or alkyl group may be linear or branched unless otherwise specified.

"Cycloalkanes" are saturated cyclic hydrocarbons with or without side chains, such as cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. If so, other identifiers may be used to indicate the presence of a particular group in the cycloalkane (a halogenated cycloalkane is one or more that replaces an equivalent number of hydrogen atoms in the cycloalkane. Indicates the presence of halogen atoms, etc.).

The word "halogen" has its usual meaning. Examples of halogens include fluorine, chlorine, bromine, and iodine.

転換率は、供給された「転換可能な」成分１モル当たりに転換されたモル数として定義される：

これらの式中、ｎは連続式反応器におけるモル流量又はバッチ式反応器におけるモル数を示す。 Mol selectivity is defined as:

Conversion rate is defined as the number of moles converted per mole of "convertible" component supplied:

In these equations, n indicates the molar flow rate in the continuous reactor or the number of moles in the batch reactor.

Any method and material similar to or equivalent to that disclosed herein may be used in the practice or experiment of the invention, but typical methods and materials are described herein.
All publications and patents referred to herein are incorporated herein by reference for purposes of explanation and disclosure, eg, the constructs and methodologies described in the publications are associated with the present invention. And may be used.

Description of INDUSTRIAL APPLICABILITY The present specification discloses a supported catalyst having an enriched alkali metal content, a method for producing such a catalyst, and the use of these catalysts in an aromatization or modification process.

Methods for Producing Supported Catalysts

Various methods for producing a supported catalyst as a supported aromatization catalyst have been disclosed and described. Such a method for producing a supported catalyst may include (or essentially consist of, or consist of):
(A) Prepare a bound zeolite base;
(B) The alkali metal-enriched zeolite carrier is produced by washing the bound zeolite base with an aqueous solution containing an alkali metal; and (c) the alkali metal-enriched zeolite carrier is impregnated with a transition metal and a halogen to provide a supported catalyst. To manufacture.

In general, any of the features of the methods disclosed herein (especially bound zeolite-based zeolites and binder components, transition metals, halogens, aqueous solutions, alkali metals, conditions under which the cleaning step is performed, impregnation steps. The conditions performed, etc.) are described independently herein, and these features may be in any combination to further describe the disclosed method. Further, unless otherwise stated, other process steps may be performed before, during, and / or after any of the steps listed in the disclosed methods. Further, supported catalysts (such as supported aromatization catalysts) produced according to any of the disclosed methods / processes are within the scope of the present disclosure and are included herein.

The steps of these methods utilizing aqueous solutions containing alkali metals are often referred to as cleaning steps, while the steps of these methods utilizing transition metals and halogens are often referred to as impregnation steps. In the cleaning step, the compositional properties of the aqueous solution and alkali metal are meant to refer to the incoming aqueous solution and alkali metal prior to contact with the bound zeolite base, unless otherwise stated. As will be readily appreciated by those skilled in the art, the composition of the aqueous solution after contact with the bound zeolite base may be significantly different from the composition of the aqueous solution containing the alkali metal.

With reference to the bound zeolite base in step (a) here, any suitable bound zeolite base may be used in the method of the present invention. Typically, the bound zeolite base may comprise an inorganic oxide, for example including a bonded middle pore and / or a large pore zeolite (aluminosilicate), an amorphous inorganic oxide, and a mixture thereof. However, it is not limited to these. Large pore zeolites often have an average pore diameter in the range of about 7 Å to about 12 Å, and examples of large pore zeolites are L-zeolites, Y-zeolites, mordenites, omega zeolites, β-zeolites and the like. , Not limited to these. Medium pore zeolites often have an average pore diameter in the range of about 5 Å to about 7 Å. Amorphous inorganic oxides may include, but are not limited to, aluminum oxide, silicon oxide, titania, and combinations thereof.

The term "zeolite" generally refers to a particular group of hydrated crystalline metal aluminosilicates. These zeolites represent a network of SiO ₄ and AlO ₄ tetrahedra in which aluminum and silicon atoms are crosslinked in a three-dimensional skeleton by sharing oxygen atoms. Within this skeleton, the ratio of oxygen atoms to the sum of aluminum and silicon atoms may be equal to 2. The skeleton exhibits negative electrical values that can be balanced by including cations such as metals, alkali metals, and / or hydrogen in the crystals.

In some embodiments, the bound zeolite base may comprise an L-type zeolite. The L-type zeolite carrier is a subgroup of zeolite carriers that may contain a molar ratio of oxides according to the formula: M _{2 / n} OAl ₂ O ₃ xSiO ₂ yH ₂ O. In the formula, "M" may be replaced with other exchangeable cations without substantially altering the basic crystal structure of the L-type zeolite, barium, calcium, strontium, lithium, magnesium, potassium, sodium. , Strontium, and / or exchangeable cations (s) such as zinc, and non-metal cations such as hydronium and ammonium ions. In the formula, "n" represents the valence of "M";"x" is greater than or equal to 2; "y" is the number of water molecules contained in the zeolite channel or interconnected voids.

In one embodiment, the bound zeolite base may comprise a bound potassium L-type zeolite, also referred to as a K / L-zeolite, and in another embodiment, the bound zeolite base may comprise a barium ion exchange L-zeolite. As used herein, the term "K / L-type zeolite" refers to an L-type zeolite in which the main cation M incorporated into the zeolite is potassium. K / L-zeolites can be cation-exchanged (eg, with barium) or impregnated with a transition metal and one or more halides to a transition metal impregnated halogenated zeolite or K / L-supported transition metal-halide. Zeolite catalysts may be produced.

In a bound zeolite base, the zeolite may bind to a support matrix (or binder), and the binder may include, but is not limited to, inorganic solid oxides, clays and the like, as well as combinations thereof. Zeolites may be attached to the binder or support matrix using any method known in the art. For example, the bound zeolite base in step (a) comprising zeolite and binder can be produced in a step comprising: mixing zeolite such as K / L-zeolite with binder such as silica, extruding or drying the mixture. And firing.

In some embodiments, the binder may comprise alumina, silica, magnesia, boria, titania, zirconia, or a mixed oxide thereof (such as aluminosilicate), or mixtures thereof, but in other embodiments, the binder. May include: montmorillonite, kaolin, cement, or a combination thereof. In certain embodiments contemplated herein, the binder may comprise silica, alumina, or a mixed oxide thereof, or silica, or alumina, or silica-alumina. Therefore, the bound zeolite base may contain silica-bound L-type zeolite such as silica-bound Ba / L-type zeolite or silica-bonded K / L-type zeolite.

The bound zeolite bases included herein may include from about 3% by weight to about 35% by weight of the binder. For example, the bound zeolite base may contain from about 5% to about 30% by weight, or from about 10% to about 30% by weight of the binder. These weight percent are based on the total weight of the bound zeolite bases, excluding transition metals and halogens, for example.

Illustrative examples of their use in bound zeolite bases and supported catalysts are US Pat. Nos. 5,196,631, 6,190,539, 6,406,614, 6,518. , 470, 6,812,180, and 7,153,801, the disclosure of which is incorporated herein by reference in its entirety.

Here, referring to step (b), which is also referred to as a washing step, the bound zeolite base may be washed with an arbitrary suitable aqueous solution containing an alkali metal (or a mixture of alkali metals) to obtain an alkali metal-enriched zeolite carrier. good. The alkali metal in the step (b) may be any of the Group 1 elements. For example, alkali metals may include potassium, rubidium, or cesium, as well as combinations thereof (or may be essentially or consist of them). In some embodiments, the alkali metal may include (or may be essentially or consist of) potassium, rubidium, or cesium.

The aqueous solution used in the cleaning step may contain any suitable form of alkali metal (or multiple metals), but in many cases the aqueous solution contains a salt of the alkali metal. Exemplary salts may include, but are not limited to, chlorides, fluorides, bromides, iodides, nitrates and the like, as well as combinations thereof. Although not bound by the following theories, it is believed that nitrates can be detrimental due to the potential for NOx formation during subsequent processing. Therefore, in a particular aspect of the invention, the aqueous solution in the washing step may contain alkali metal halide salts such as potassium chloride, rubidium chloride, or cesium chloride, as well as mixtures thereof.

As will be appreciated by those skilled in the art, in addition to water and alkali metals, the aqueous solution used in the cleaning step may contain other components. However, in some embodiments, the cleaning step may include contacting the bound zeolite base with an aqueous solution, which essentially consists of an alkali metal salt and water, or an alkali metal salt and deionized water. Or consists of them. In these and other embodiments, the aqueous solution used in the cleaning step (and optionally any step in the method after step (a)) is substantially free of basic compounds (such as hydroxides). And / or substantially free of ammonia or ammonium-containing compounds, and / or substantially free of sulfur or any sulfur-containing compound. In these situations, "substantially free" means less than 100 ppmw (weight-based ppm), more typically less than 75 ppmw, less than 50 ppmw, less than 25 ppmw, or less than 10 ppmw, regardless of any of these materials. Means to include. Thus, the individual amounts of any of these materials in aqueous solution (or used in any step in the method after step (a)) are about 0.1 ppmw-100 ppmw, about 0.1 ppmw-75 ppmw, about. It is believed to be in the range of 1 ppmw to 100 ppmw, about 1 ppmw to about 75 ppmw, about 0.1 ppmw to about 50 ppmw, about 1 ppmw to about 50 ppmw, or about 1 ppmw to about 25 ppmw. Without wishing to be bound by theory, cleaning steps in the disclosed methods for producing supported catalysts, as these materials can adversely affect catalytic activity, catalytic selectivity, catalytic lifetime and / or catalytic deactivation. It is believed that the substantial absence of these materials during the period can be beneficial. Moreover, although not required, the aqueous solution (and any step in the method after step (a)) may be substantially free of sodium or sodium-containing compounds, i.e., less than 100 ppmw (% by weight) sodium. Alternatively, it may contain a sodium-containing compound. As described above, the amount may be, for example, less than 75 ppmw, less than 50 ppmw, less than 25 ppmw, in the range of about 0.1 ppmw to 100 ppmw, in the range of about 0.1 ppmw to about 75 ppmw, or in the range of about 1 ppmw to about 75 ppmw. It is considered that there may be.

Thus, in some embodiments, the alkali metal used in the cleaning step is not sodium but one or more of potassium, rubidium, and / or cesium. As an addition or alternative, step (b) of the disclosed method may be the only step in the method of making a carrier catalyst utilizing an alkali metal, eg, an alkali metal salt.

In the washing step, the pH of the aqueous solution is not limited to any particular range. However, in general, the pH may be in the range of 6-8, depending on the alkali metal salts used and their respective concentrations.

The amount of alkali metal in aqueous solution is often not limited to, but may be less than about 5 M (mol / L). For example, the aqueous solution may have an alkali metal at a concentration of less than about 1M, less than about 0.75M, less than about 0.5M, less than about 0.3M, less than about 0.25M, or less than about 0.2M. .. Accordingly, the appropriate range of alkali metal concentration may include, but is not limited to, the following ranges: about 0.01M to about 5M, about 0.01M to about 1M, about 0.01M to 0. 5M, about 0.01M to about 0.45M, about 0.01M to about 0.3M, about 0.01M to about 0.25M, about 0.01M to about 0.2M, about 0.05M to about 1M, About 0.05M to about 0.5M, about 0.05M to about 0.45M, about 0.05M to about 0.3M, about 0.05M to about 0.25M, or about 0.05M to about 0.2M. Such.

Unexpectedly, it was found that low concentrations of cesium in the washing process could be beneficial in improving catalytic activity and selectivity. In these embodiments, the concentration of cesium (or cesium salt) in the aqueous solution is about 0.01M to about 0.25M, about 0.01M to about 0.2M, about 0.01M to about 0.15M, about 0. .025M to about 0.25M, about 0.025M to about 0.2M, about 0.025M to about 0.15M, about 0.05M to about 0.25M, or about 0.05M to about 0.2M It may be inside.

It was also unexpectedly found that slightly higher concentrations of potassium in the washing process could be beneficial in improving catalytic activity and selectivity. In these embodiments, the concentration of potassium (or potassium salt) in the aqueous solution is about 0.1M to about 0.45M, about 0.15M to about 0.45M, about 0.15M to about 0.35M, about 0. It may be in the range of .15M to about 0.3M, about 0.2M to about 0.45M, about 0.2M to about 0.35M, or about 0.2M to about 0.3M.

Cleaning steps involving alkali metals may be performed at various temperatures and periods. For example, the cleaning step may be performed within the following cleaning temperatures: about 15 ° C to 95 ° C; or about 15 ° C to about 80 ° C; or about 15 ° C to about 70 ° C; or about. 15 ° C to 65 ° C; or about 20 ° C to about 95 ° C; or about 20 ° C to about 80 ° C; or about 20 ° C to about 70 ° C; or about 20 ° C to about 50 ° C; or about 30. ° C to about 80 ° C; or about 30 ° C to about 70 ° C; or about 30 ° C to about 50 ° C; or about 25 ° C to about 55 ° C; or about 30 ° C to about 45 ° C. In these and other embodiments, these temperature ranges also mean that the cleaning step is performed at a series of different temperatures within each range instead of a single fixed temperature.

The cleaning step containing an alkali metal may be carried out by performing one or more cleaning cycles containing an alkali metal, for example 1 to 4 cleaning cycles, 2 to 8 or 2 to 4 cleaning cycles. good. Thus, for example, the cleaning step may include 1 to 4 cleaning cycles, 2 to 8 cleaning cycles, or 2 to 4 cleaning cycles, each cleaning cycle alone from about 1 minute to. It is within the range of about 6 hours, about 5 minutes to about 2 hours, about 10 minutes to about 45 minutes, or about 10 minutes to about 30 minutes.

The duration of a single wash cycle containing alkali metals is not limited to any particular time. Therefore, the cleaning step may be performed, for example, for a period ranging from a minimum of 1 to 5 minutes to a maximum of 2 to 4 hours, 6 to 8 hours, or more. The appropriate wash cycle time may depend on other variables, for example, the wash temperature, the amount of alkali metal in aqueous solution, and the number of wash cycles. However, in general, the cleaning cycle step is about 1 minute to about 6 hours, for example, about 1 minute to about 2 hours, about 5 minutes to about 2 hours, about 5 minutes to about 1 hour, about 10 minutes to about. It may be carried out within the range of 1 hour, about 5 minutes to about 45 minutes, about 10 minutes to about 45 minutes, or about 10 minutes to about 30 minutes.

In general, the amount of aqueous solution used in the washing step (or each washing cycle) -including alkali metals-is not particularly limited relative to the amount of bound zeolite base. In one aspect, for example, the ratio of the weight of the aqueous solution to the weight of the bound zeolite base may be in the range of about 0.4: 1 to about 50: 1 or about 0.5: 1 to about 25: 1. .. In another aspect, the ratio of the weight of the aqueous solution to the weight of the bound zeolite base may be in the range of about 0.4: 1 to about 10: 1 or about 0.5: 1 to about 10: 1. In yet another embodiment, the ratio of the weight of the aqueous solution to the weight of the bound zeolite base may be in the range of about 0.5: 1 to about 8: 1 or about 0.5: 1 to about 5: 1. In yet another embodiment, the ratio of the weight of the aqueous solution to the weight of the bound zeolite base may be in the range of about 1: 1 to about 15: 1 or about 1: 1 to about 5: 1.

Cleaning steps containing alkali metals may be performed using any suitable technique and equipment. For example, the bound zeolite base may be placed in a container or tank and then filled with sufficient aqueous solution containing an alkali metal to exceed the level of the bound zeolite base in the container or tank. Optionally, agitation may be performed in the container and tank to increase the contact between the bound zeolite base in the aqueous solution and the alkali metal. Alternatively, the bound zeolite base may be placed on a fixed bed or a packed bed, and the aqueous solution may be brought into contact with the bound zeolite by flowing the aqueous solution through the bed of the bound zeolite base. As will be appreciated by those skilled in the art, other suitable techniques and equipment may be used in the cleaning process, such techniques and equipment are included herein.

Although not required, the cleaning step may be performed by performing one or more alkali metal-free cleaning cycles, eg, 1 to 4 cleaning cycles. The cleaning conditions may be the same as the cleaning process with an alkali metal described herein.

In step (b) of the method for producing a supported catalyst disclosed herein, the bound zeolite base may be washed with an aqueous solution containing an alkali metal to produce a zeolite carrier "enriched" with an alkali metal. In fact, the cleaning step may enrich the bound zeolite base with any suitable or desired amount of alkali metal, the enrichment amount being the amount of alkali metal in the alkali metal enriched zeolite carrier and the bound zeolite base. It is the difference from the amount of alkali metal in. The number of moles of bound zeolite base enriched in the cleaning step may be: but not limited to: about 0.03 mol to about 1.5 mol per kg of bound zeolite base (or per kg of alkali metal enriched zeolite carrier). Molly alkali metal; or about 0.03 mol to about 1 mol of alkali metal per kg of bound zeolite base (or alkali metal enriched zeolite carrier); or per 1 kg of bound zeolite base (or alkali metal enriched zeolite) Approximately 0.03 mol to approximately 0.7 mol of alkali metal per kg of carrier; or approximately 0.05 mol to approximately 1 mol of alkali metal per 1 kg of bound zeolite base (or per 1 kg of alkali metal enriched zeolite carrier); Alternatively, about 0.1 mol to about 1.2 mol of alkali metal per kg of bound zeolite base (or per kg of alkali metal enriched zeolite carrier); or per kg of bound zeolite base (or per kg of alkali metal enriched zeolite carrier). ) About 0.1 mol to about 0.9 mol of alkali metal; or about 0.2 mol to about 0.8 mol of alkali metal per kg of bound zeolite base (or per kg of alkali metal enriched zeolite carrier); Or, about 0.3 mol to about 0.7 mol of alkali metal per 1 kg of bound zeolite base (or per 1 kg of alkali metal enriched zeolite carrier). As an example, bound zeolite base (without cesium) in an aqueous solution containing a cesium salt (at any temperature, cleaning time disclosed herein, and in one or more cleaning cycles performed at relative amounts of the aqueous solution). ) By washing, a cesium-enriched zeolite carrier containing about 0.5 mol of cesium per 1 kg of bound zeolite base (or about 0.5 mol of cesium per 1 kg of cesium-enriched zeolite carrier) may be produced. As another example, a bound zeolite base (eg, a bound K / L-zeolate containing about 3 mol of potassium per kg of bound K / L-zeolite) in an aqueous solution containing a potassium salt (optional as disclosed herein). By washing with one or more washing cycles performed at the temperature, washing time, and relative amount of aqueous solution), approximately 3.1 mol of potassium (or potassium enriched K /) per kg of bound K / L-zeolite. A potassium-enriched zeolite carrier containing (about 3.1 mol) per kg of L-zeolite carrier may be produced.

As will be readily appreciated by those skilled in the art, alkali metal enrichment due to alkali metal contamination during cleaning of bound zeolite bases may be achieved by various combinations of conditions that may be used in step (b). Once the desired level of alkali metal enrichment is selected, the results include the number of cleaning cycles, cleaning time, cleaning temperature, molar concentration of alkali metal in aqueous solution, relative amount of aqueous solution based on the weight of bound zeolite base, etc. It may be achieved by many different combinations of.

In addition to producing the alkali metal enriched zeolite carrier in the washing step, the amount of sodium may be reduced if the bound zeolite base contains sodium and no aqueous solution. In these situations, the resulting alkali metal enriched zeolite carrier may contain less than about 0.35% by weight of sodium, or less than about 0.3% by weight of sodium, based on the weight of the alkali metal enriched zeolite carrier. .. In some embodiments, the amount of sodium in the alkali metal enriched zeolite carrier is from about 0.03% to about 0.35% by weight, from about 0.05% to about 0, based on the total weight of the zeolite carrier. .3% by weight, about 0.01% by weight to about 0.25% by weight, or about 0.03% by weight to about 0.2% by weight of sodium.

If the alkali metal enriched zeolite carrier is produced in step (b), the alkali metal enriched zeolite carrier may be dried and / or fired prior to step (c), if desired. When both drying and calcining are performed, the alkali metal enriched zeolite carrier is typically dried and then calcined.

When a drying step is performed, the drying step usually involves contacting the alkali metal enriched zeolite carrier with a dry gas stream, which comprises (or becomes intrinsically from the following, or from the following): Will): inert gas (such as nitrogen), oxygen, air, or any mixture or combination thereof; or nitrogen; or helium; or neon; or argon; or oxygen; or any combination thereof. .. Although not limited, the drying step may generally be carried out in the following drying temperature range: from about 80 ° C to about 200 ° C; or from about 100 ° C to about 200 ° C; or from about 85 ° C to about 175 ° C. Also, or from about 100 ° C to about 150 ° C. In these and other embodiments, these temperature ranges also imply that the drying step may be carried out at a series of different temperatures within each range rather than at a single fixed temperature.

The duration of the drying process is not limited to any particular duration. Typically, the drying step may be carried out for a period ranging from a minimum of 30 minutes to a maximum of 8 hours (or more), and more typically, the drying step may be carried out for about 1 hour to about 8 hours, eg, for example. It may be performed for a period that may be within the range of about 1 hour to about 7 hours, about 1 hour to about 6 hours, about 2 hours to about 7 hours, or about 2 hours to about 6 hours.

When the firing step is performed, the firing step is performed at various temperatures and periods. Typical peak firing temperatures often fall within the range of about 315 ° C to about 600 ° C, for example about 375 ° C to about 600 ° C, about 400 ° C to about 550 ° C, or about 425 ° C to about 500 ° C. In these and other embodiments, these temperature ranges are also performed at a series of different temperatures (eg, initial firing temperature, peak firing temperature) within which the firing step belongs, rather than a single fixed temperature. It means to include possible situations. For example, the firing step may be started at the same initial temperature as the drying temperature in the drying step. After that, the firing temperature may be raised in the range of about 375 ° C to about 600 ° C, for example, to the peak firing temperature over time.

The period of the firing step is not limited to any particular period. Therefore, the firing step may be performed, for example, for a period ranging from a minimum of 30 to 45 minutes to a maximum of 10 to 12 hours or more. The appropriate calcination time may depend on, among other variables, for example, the initial / peak calcination temperature and whether or not the drying step is used. However, in general, the firing step is about 45 minutes to about 12 hours, for example, about 1 hour to about 12 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, or about 1 hour to about. It may be done for a period that can be within the range of 3 hours.

The calcination step may be performed in a calcination gas stream containing (or essentially consisting of or consisting of) an inert gas (such as nitrogen), oxygen, air, or any mixture or combination thereof. good. In some embodiments, the calcined gas stream may contain air, but in other embodiments, the calcined gas stream may comprise a mixture of air and nitrogen. Further, in certain embodiments, the calcined gas stream may be an inert gas such as nitrogen and / or argon.

Here, referring to step (c) of the method for producing a supported catalyst, the supported catalyst may be produced by impregnating an alkali metal-enriched zeolite carrier with a transition metal and halogen. Non-limiting examples of suitable transition metals may include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, silver, copper, etc., or combinations of two or more transition metals. good. In one embodiment, the transition metal may comprise a Group 8-11 transition metal or a Group 8-10 transition metal (s), and in another embodiment, the transition metal may comprise platinum (Pt). .. In yet another embodiment, the alkali metal enriched zeolite carrier is impregnated with only one transition metal, the transition metal being platinum.

The transition metal is appropriately dispersed in the carrier by being added to the zeolite carrier by an appropriate method or technique well known to those skilled in the art. One such method involves mixing the alkali metal enriched zeolite carrier with the transition metal containing compound, even if the transition metal containing compound is present in a solution of any suitable solvent such as water. good. Exemplary and non-limiting examples of transition metal-containing compounds suitable for use in impregnating bound zeolite bases with platinum include tetraamine platinum (II) chloride, tetraamine platinum (II) nitrate, platinum (II). Examples include, but are not limited to, acetylacetonate, platinum (II) chloride, ammonium (II) tetrachloroplatinate, platinum chloride, platinum (II) nitrate, and mixtures or combinations thereof.

In one aspect, the carrier catalyst may consist of about 0.1% by weight to about 10% by weight of the transition metal. In another aspect, the carrier catalyst may consist of about 0.2% by weight to about 5% by weight of the transition metal. In yet another embodiment, the carrier catalyst may consist of about 0.3% by weight to about 3% by weight of the transition metal, or about 0.3% by weight to about 2% by weight of the transition metal. These weight percent are based on the total weight of the supported catalyst.

When the transition metal contains platinum, the carrier catalyst is about 0.1% by weight to about 10% by weight platinum; or about 0.2% by weight to about 5% by weight platinum; or about 0.3% by weight to. It consists of about 3% by weight platinum; or about 0.3% by weight to about 2% by weight platinum. In certain embodiments contemplated herein, the supported catalyst may comprise platinum on an alkali metal enriched bonded K / L zeolite.

In addition to impregnating the alkali metal enriched zeolite carrier with a transition metal such as platinum, the alkali metal enriched zeolite carrier may be impregnated with halogen to produce a supported catalyst. Typically, the halogen comprises chlorine and / or fluorine. Therefore, chlorine or fluorine may be used alone, or both chlorine and fluorine may be used. The halogen (1 or more) may be added to the zeolite carrier before, during and / or after the addition of the transition metal.

Halogen may be added to the zeolite carrier by any suitable method or technique known to those of skill in the art. One such method involves contacting or mixing the alkali metal enriched zeolite carrier with chlorine-containing and / or fluorine-containing compounds in any order or order. In one aspect, the alkali metal enriched zeolite carrier may be mixed with a solution of the chlorine-containing compound and / or the fluorine-containing compound in any suitable solvent. Exemplary and non-limiting examples of chlorine-containing compounds are hydrochloric acid, carbon tetrachloride, tetrachloroethylene, chlorobenzene, methyl chloride, methylene chloride, chloroform, allyl chloride, trichloroethylene, chloramine, chlorine oxide, chloric acid, chlorine dioxide, monochloride. Dichlorin, dichlorine heptaoxide, chloric acid, perchloric acid, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, methyltriethylammonium chloride, etc., and combinations thereof are listed. Be done. Illustrative and non-limiting examples of fluorine precursors include hydrofluoric acid, 2,2,2-trifluoroethanol, tetrafluoroethylene, carbon tetrafluoride, carbon trifluoride, fluoromethane, heptafluoropropane, Decafluorobutane, hexafluoroisopropanol, tetrafluoropropanol, pentafluoropropanol, hexafluorophenylpropanol, perfluorobutyl alcohol, hexafluoro-2-propanol, pentafluoro-1-propanol, tetrafluoro-1-propanol, 1,1, 1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrafluoride Examples include propylammonium, tetrabutylammonium fluoride, methyltriethylammonium fluoride and the like, and combinations thereof.

In another aspect, the alkali metal enriched zeolite carrier may be impregnated with halogen in the gas phase. For example, the zeolite carrier may be in contact with a chlorine-containing stream containing a chlorine-containing compound and / or a fluorine-containing stream containing a fluorine-containing compound in any order or order. Suitable chlorine-containing compounds and fluorine-containing compounds include those listed above, in addition to chlorine gas (Cl ₂ ) and fluorine gas (F ₂ ).

Based on the total weight of the carrier catalyst, if chlorine (Cl) is present, the amount of chlorine is often from about 0.05% to about 5% by weight, from about 0.1% to about 1.5% by weight, It may be in the range of about 0.2% by weight to about 1% by weight, or about 0.5% by weight to about 1.5% by weight. Similarly, based on the total weight of the carrier catalyst, if fluorine (F) is present, the amount of fluorine is often from about 0.05% to about 5% by weight, from about 0.1% to about 1.5% by weight. It may be in the range of% by weight, about 0.2% by weight to about 1% by weight, or about 0.5% by weight to about 1.5% by weight.

After the carrier catalyst is produced in step (c), the carrier catalyst may be dried and / or calcined, if necessary. If both drying and firing are performed, the supported catalyst is typically dried and then fired. Any suitable temperature, pressure, duration and atmosphere may be used in the drying and baking steps. In some embodiments, the step of drying the supported catalyst may be performed in the same manner as the step of drying the alkali metal enriched zeolite carrier described above (eg, temperature range, time range, inert atmosphere or oxidizing atmosphere). good. In some embodiments, the drying step may be performed under any suitable depressurization, such as less than about 125 torr, less than about 100 torr, or less than about 50 torr.

The supported catalyst in step (c) may be calcined. When the firing step is performed, the firing step may be performed at various temperatures and periods. Typical peak firing temperatures are in the range of about 175 ° C to about 450 ° C, for example about 200 ° C to about 400 ° C, about 225 ° C to about 350 ° C, or about 250 ° C to about 300 ° C. In these and other embodiments, these temperature ranges are also performed at a series of different temperatures (eg, initial firing temperature, peak firing temperature) within which the firing step belongs, rather than a single fixed temperature. It means to include possible situations. For example, the firing step may be started at the same initial temperature as the drying temperature in the drying step. After that, the firing temperature may be raised in the range of about 375 ° C to about 600 ° C, for example, to the peak firing temperature over time.

The period of the firing step is not limited to any particular period. Therefore, the firing step may be performed, for example, for a period ranging from a minimum of 30 to 45 minutes to a maximum of 10 to 12 hours or more. The appropriate calcination time may depend on, among other variables, for example, the initial / peak calcination temperature and whether or not the drying step is used. However, in general, the firing step is about 45 minutes to about 12 hours, for example, about 1 hour to about 12 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, or about 1 hour to about. It may be done for a period that can be within the range of 3 hours.

The calcination step may be performed in a calcination gas stream containing (or essentially consisting of or consisting of) an inert gas (such as nitrogen), oxygen, air, or any mixture or combination thereof. good. In some embodiments, the calcined gas stream may contain air, but in other embodiments, the calcined gas stream may comprise a mixture of air and nitrogen. Further, in certain embodiments, the calcined gas stream may be an inert gas such as nitrogen and / or argon.

The method for producing the supported catalyst disclosed herein may further include a reduction step after step (c). This reduction step may include contacting the carrier catalyst with a stream of reducing gas containing hydrogen. Often, the reducing gas stream contains molecular hydrogen alone or with an inert gas such as helium, neon, argon, nitrogen, which comprises a combination of two or more of these inert gases. In certain embodiments, the reducing gas stream may include (or essentially consist of, or may consist of) molecular hydrogen and nitrogen. Further, the molecular hydrogen may be the main component (more than 50 mol%) of the reducing gas stream, but in other embodiments, the molecular hydrogen may be a trace component (5 to 35 mol%).

The reduction step may be carried out at various temperatures and periods. For example, the reduction step is about 100 ° C. to about 700 ° C.; or about 200 ° C. to about 600 ° C.; or about 200 ° C. to about 575 ° C.; or about 350 ° C. to about 575 ° C.; or about 400 ° C. to About 550 ° C; Alternatively, it may be carried out within a reduction temperature range of about 450 ° C to about 550 ° C. In these and other embodiments, these temperature ranges also imply that the reduction step is performed at a series of different temperatures within each range, rather than at a single fixed temperature.

The duration of the reduction step is not limited to any particular duration. Therefore, the reduction step may be performed, for example, for a period ranging from a minimum of 1 hour to a maximum of 48 to 72 hours or more. For example, the reduction step is within the range of about 2 hours to about 48 hours, about 3 hours to about 36 hours, about 5 hours to about 36 hours, about 2 hours to about 30 hours, or about 10 hours to about 30 hours. It may be done during a period that may be present.

In some embodiments, the carrier catalyst may contain from about 0.05 mol to about 1.5 mol moles of alkali metal per kg of carrier catalyst, whereas in other embodiments, the carrier catalyst may contain about 0.05 mol per kg of carrier catalyst. It may contain from mol to about 1 mol of alkali metal. For example, the supported catalyst is about 0.05 mol to about 0.7 mol of alkali metal per 1 kg of supported catalyst, about 0.1 mol to about 0.9 mol of alkali metal per 1 kg of supported catalyst, and about 0 per kg of supported catalyst. It may contain from 2 mol to about 0.8 mol of alkali metal, or from about 0.3 mol to about 0.7 mol of alkali metal per kg of supported catalyst. In these and other embodiments, the carrier catalyst is an alkali metal of from about 10,000 ppm to about 125,000 ppm (by weight; from about 1 wt% to about 12.5 wt%), eg, based on the total weight of the carrier catalyst. , About 20,000 ppm to about 100,000 ppm of alkali metal, about 25,000 ppm to about 110,000 ppm of alkali metal, about 30,000 ppm to about 90,000 ppm of alkali metal, or about 40,000 ppm to about 85,000 ppm. Alkali metals may be contained.

The supported catalyst produced according to the present invention may have a smaller surface area than the catalyst obtained by washing the bound zeolite base with an aqueous solution containing no alkali metal under the same catalyst production conditions. Exemplary and non-limiting examples of suitable ranges of surface area of the supported catalyst are from about 100 m ² / g to about 170 m ² / g, from about 100 m ² / g to about 150 m ² / g, from about 105 m ² / g to about. Includes 170 m ² / g, or about 105 m ² / g to about 160 m ² / g. Similarly, exemplary and non-limiting examples of suitable ranges of surface area of alkali metal enriched zeolite carriers are from about 120 m ² / g to about 250 m ² / g, from about 130 m ² / g to about 230 m ² / g. Includes about 150 m ² / g to about 240 m ² / g, or about 160 m ² / g to about 220 m ² / g.

Similarly, a supported catalyst produced according to the present invention may have a smaller pore volume than the catalyst obtained by washing the bound zeolite base with an aqueous solution containing no alkali metal under the same catalyst production conditions. good. Exemplary and non-limiting examples of suitable ranges for the pore volume of the carrier catalyst are from about 0.015 cc / g to about 0.05 cc / g, from about 0.02 cc / g to about 0.045 cc / g, about 0.045 cc / g. It contains 0.025 cc / g to about 0.045 cc / g and about 0.0265 cc / g to about 0.045 cc / g. Similarly, exemplary and non-limiting examples of suitable ranges of pore volume of alkali metal enriched zeolite carriers are from about 0.025 cc / g to about 0.08 cc / g, from about 0.03 cc / g to about. It contains 0.07 cc / g, from about 0.04 cc / g to about 0.08 cc / g, or from about 0.045 cc / g to about 0.075 cc / g.

Advantageously, the alkali metal enrichment-supported catalysts disclosed herein may have excellent platinum dispersity, despite the reduced surface area and pore volume. Often, the platinum dispersity ranges from about 50% to about 70%, about 52% to about 62%, about 55% to about 70%, about 55% to about 65%, or about 55% to 60%. You may.

Aromatization catalyst reforming process

Also included herein are various methods for modifying hydrocarbons. Such a reforming process may include (or may consist essentially of, or may consist of): carrying an aromatication catalyst under reforming conditions in the reactor system as a hydrocarbon feedstock. Produces aromatic products upon contact with. The supported aromatization catalysts used in the modification process are manufactured by any of the supported catalysts disclosed herein and / or any method for producing the supported catalysts disclosed herein. May be good.

Reactor systems for reforming and the respective reforming conditions are well known to those of skill in the art, for example, US Pat. Nos. 4,456,527, 5,389,235, 5,401, No. 386, No. 5,401,365, No. 6,207,042, and No. 7,932,425 are described, and the disclosure contents thereof are described in the present specification as a whole by reference. Will be incorporated into.

Similarly, typical hydrocarbon sources are disclosed in these references. In many cases, the hydrocarbon source may be naphtha stream or light naphtha stream. In certain embodiments, the hydrocarbon feedstock may comprise a non-aromatic hydrocarbon, eg, the hydrocarbon feedstock may be a C6 _{- C9} alkane and / or a cycloalkane, or a C6 _{- C8} alkane and / or. It may contain cycloalkanes (hexane, heptane, cyclohexane, etc.) and the like.

The supported catalysts described herein may be characterized by the _TEOR (Experiment End Temperature) disclosed herein, which is often from about 499 ° C (930 ° F) to about 530 ° C (986). ° F), about 499 ° C (930 ° F) to about 524 ° C (975 ° F), about 499 ° C (930 ° F) to about 515 ° C (959 ° F), and about 501 ° C (934 ° F). It may be in the range of about 521 ° C (970 ° F).

In addition to the yields of aromatic compounds quantified by these catalysts- _TEORs , the alkali metals are supported without enrichment, despite the reduction in surface area and pore volume of the alkali metal enriched supporting catalysts. Corresponds to the catalyst-may also have an unexpected improvement in selectivity. For example, the supported catalysts disclosed herein have greater benzene selectivity (or greater benzene selectivity) than the catalysts obtained by washing the bound zeolite base with an aqueous solution without alkali metals under the same catalyst production and aromatization reaction conditions. It may have toluene selectivity). Such comparison of catalyst selectivity means having the same amount of platinum and halogen in the catalyst, using the same bound zeolite base, experimenting with the same equipment under the same experimental methods and conditions, and the like. The other difference is the use (or no use) of alkali metals during the cleaning process.

Typical, but not limited to, benzene selectivity (and toluene selectivity) is often from about 0.91 to about 0.97, about 0 when deciding to use the experimental procedures and conditions described herein. .92 to about 0.98, about 0.92 to about 0.97, about 0.94 to about 0.98, about 0.95 to about 0.98, about 0.95 to about 0.975, or about It may be in the range of 0.95 to about 0.97.

The invention is further described by the following examples, but they should by no means be construed as limiting the scope of the invention. After reading the description of the present specification, various other embodiments, embodiments, modifications, and equivalents thereof have been conceived by those skilled in the art without departing from the spirit of the present invention or the appended claims. Can be done.

The supported catalysts were tested for their performance in the aromatization reaction by the following general procedure. The supported aromatization catalyst was crushed, sieved into approximately 25-45 meshes, and 1 cc of the sieved supported catalyst was placed in a temperature controlled furnace with a 3/8 inch outer diameter stainless steel reactor vessel. .. After reducing the carrier catalyst under a molecular hydrogen stream, the feed stream of aliphatic hydrogen and molecular hydrogen is applied at a pressure of 100 psig, H ₂ : hydrocarbon with a molar ratio of 1.3: 1, and a liquid space of 12 hours ^-1 . Catalyst performance data over time was obtained by introduction into the reaction vessel at a rate (LHSV). The aliphatic hydrocarbon raw material contained ₆ convertible C species having a mole fraction of about 0.61 and ₇ convertible C species having a 0.21 mole fraction. The rest were _C8 + aromatic compounds classified as non-convertible, and highly branched isomers. The reactor effluent composition was analyzed by gas chromatography to determine the amounts of a number of feedstock and product components present, including benzene and toluene (for selectivity calculation).

The catalytic performance was quantified by the temperature required to obtain a yield of 63% by weight of the aromatic compound. _TEOR (experiment end temperature) was the temperature at which the desired yield was obtained at the end of the experiment, which was about 40 hours.
The alkali metal content (number of moles of alkali metal) of the alkali metal enriched zeolite carrier was determined by XRF or ICP. The weight ratios of Pt, Cl, and F were determined by X-ray fluorescence (XRF). The surface area was determined by the BET method, and the pore volume was determined by the t-plot method. The platinum dispersity was determined by CO chemisorption.
[Examples 1 to 5]

A standard bound KL-zeolite base consisting of about 17% by weight silica binder was used as the starting material for Examples 1-5. The bound zeolite base was washed with either water (Example 1) or water containing 0.1 M alkali metal salts (NaCl, KCl, RbCl or CsCl-Examples 2-5). The cleaning conditions consisted of three cleaning cycles, each performed at 100 ° F. for 20 minutes with cleaning water (with or without alkali metal) weighing 2.5 times the weight of the bound zeolite base. Washing was done in batch with _N2 bubbling to stir the mixture.

Table I summarizes the metal analysis of alkali metal enriched zeolite carriers after drying and calcination in air at 250 ° F and 900 ° F. Alkali metal cleaning steps with rubidium or cesium (Examples 4-5) have significantly reduced the amount of sodium in the carrier and each have about 0.5 mol (per kg) of alkali in the alkali metal enriched zeolite carrier. Brought metal. Alkaline washing with potassium also reduced the amount of sodium in the carrier. As shown in Examples 4-5, alkaline cleaning with rubidium or cesium also reduced the potassium content of the carrier.

The alkali metal enriched zeolite carrier was subsequently impregnated with platinum and halogen, dried (95 ° C.) and calcined (900 ° F.) to form a supported aromatization catalyst. Pt, Cl, and F were added in one step by the initial wetting technique. Finally, the addition amounts of Pt, Cl, and F were all about 1% by weight. Table II summarizes the pore volume and surface area of the alkali metal-enriched zeolite carrier and the supported catalyst after drying / firing, and the platinum dispersibility of the supported catalyst. In Table II, "carrier" is an alkali metal enriched zeolite carrier prior to the addition of platinum and halogen, and "catalyst" is a final supported catalyst containing platinum and halogen. In general, the alkali metal cleaning step using KCl, RbCl, or CsCl (Examples 3 to 5) uses a cesium-enriched carrier and a cesium-enriched carrier having the smallest pore volume and surface area. The surface area and pore volume of enriched zeolite carriers and supported catalysts were reduced. However, despite the effects of the alkali metal cleaning step on pore volume and surface area, the dispersion of platinum on the supported catalyst was similar for each of Examples 1-5.

Further experiments were performed with potassium and cesium as in Examples 3 and 5, respectively, and the molar concentration of alkali metal in the wash water changed from 0.05 M to 0.3 M, respectively. FIG. 1 shows the effect of the molar concentrations of potassium and cesium in the aqueous solution used to wash the bound zeolite base on the pore volumes of the alkali metal enriched zeolite carrier and the supported catalyst. In general, as the alkali metal concentration increased, the pore volume decreased, but the decrease was less pronounced in the supported catalyst compared to the decrease in the alkali metal enriched zeolite carrier.

At the same alkali metal concentration in the wash water in the range of 0.05 M to 0.3 M, FIG. 2 shows the effect of the alkali metal concentration on the platinum dispersity on the supported catalyst. Unexpectedly, the platinum dispersity with potassium was relatively unaffected over the entire concentration range, but with cesium the platinum dispersity was significantly reduced at higher 0.2-0.3M concentrations. did.

The supported catalysts of Examples 1-5 were evaluated for their relative performance in the aromatization reaction, as characterized in Tables I and II. Unexpectedly, considering the reduction in surface area and pore volume of the alkali metal enrichment-supported catalysts of Examples 3-5 (see Table II), the yield of aromatic compounds measured by _TEOR in Table III is It was the same as each of Examples 1-5. However, Table III shows that the alkali metal enriched carrier catalysts of Examples 3-5 show an unexpected improvement in benzene selectivity, and that cesium enrichment increases the benzene selectivity of the carrier catalyst by 96% or more. ing.

Additional aromatization experiments were performed using potassium and cesium-enriched supported catalysts, as in Examples 3 and 5, with alkali metal molar concentrations from 0.05 M to 0.3 M, respectively. changed. FIG. 3 shows the effect of the molar concentration of cesium in the aqueous solution used to wash the bound zeolite base on benzene selectivity, toluene selectivity, and the _TEOR of the resulting carrier catalyst. Surprisingly, cesium concentrations below 0.2M provide a beneficial combination of improved benzene selectivity and improved toluene selectivity and are identical compared to the reference (no alkali metals used in the cleaning process). It has been found that the temperature of ( _TEOR ) is required to obtain the desired aromatic compound yield.

Similarly, FIG. 4 shows the effect of the molar concentration of potassium in the aqueous solution used to wash the bound zeolite base on benzene selectivity, toluene selectivity, and the _TEOR of the resulting carrier catalyst. Surprisingly, potassium concentrations above 0.1 M provide a beneficial combination of improved benzene selectivity and improved toluene selectivity, as compared to the reference (without the use of alkali metals in the cleaning process), identical. It was found that the temperature ( _TEOR ) was required to obtain the desired aromatic compound yield (the effect on temperature is not clear).

The present invention has been described above in connection with a number of embodiments and specific embodiments. Many variants will be obvious to those of skill in the art in the light of the detailed description above. All such obvious variations are within the fully intended scope of the appended claims. Other embodiments of the invention may include, but are not limited to, (the embodiments are described as "contains", but alternatives are "consisting of" or "consisting of". May be there).
[Aspect 1]

It is a method for manufacturing a supported catalyst.
(A) Prepare a bound zeolite base;
(B) The alkali metal-enriched zeolite carrier is produced by washing the bound zeolite base with an aqueous solution containing an alkali metal; and (c) the alkali metal-enriched zeolite carrier is impregnated with a transition metal and a halogen to provide a supporting catalyst. Methods involving manufacturing.
[Aspect 2]

The method of aspect 1, wherein the alkali metal comprises potassium, rubidium, cesium, or a combination thereof.
[Aspect 3]

The method according to aspect 1 or 2, wherein the aqueous solution contains an alkali metal salt.
[Aspect 4]

The method according to any one of the above-described embodiments, wherein the aqueous solution contains an alkali metal chloride salt.
[Aspect 5]

The method according to any one of aspects 1 to 4, wherein the alkali metal contains potassium.
[Aspect 6]

The method according to any one of aspects 1 to 4, wherein the alkali metal comprises rubidium.
[Aspect 7]

The method according to any one of aspects 1 to 4, wherein the alkali metal contains cesium.
[Aspect 8]

Bound Zeolite The method according to any one of the above embodiments, wherein the base comprises a zeolite and a binder.
[Aspect 9]

Based on the total weight of the bound zeolite base, the bound zeolite base is any weight percent binder disclosed herein, eg, 3% to about 35% by weight, or about 5% to about 30% by weight. 8. The method of aspect 8, comprising a binder.
[Aspect 10]

8. The method of aspect 8 or 9, wherein the binder comprises an inorganic solid oxide, clay, or a combination thereof.
[Aspect 11]

8. The method of aspect 8 or 9, wherein the binder comprises alumina, silica, magnesia, bolia, titania, zirconia, a mixed oxide thereof, or a mixture thereof.
[Aspect 12]

8. The method of aspect 8 or 9, wherein the binder comprises silica.
[Aspect 13]

8. The method of aspect 8 or 9, wherein the binder comprises montmorillonite, kaolin, cement, or a combination thereof.
[Aspect 14]

Bound Zeolite The method according to any one of the aforementioned embodiments, wherein the base comprises a bound L-zeolite.
[Aspect 15]

The method according to any one of aspects 1 to 13, wherein the bound zeolite base comprises bound Ba / L-zeolite.
[Aspect 16]

The method according to any one of aspects 1 to 13, wherein the bound zeolite base comprises a bound K / L-zeolite.
[Aspect 17]

The method according to any one of aspects 1 to 12, wherein the bound zeolite base comprises a silica bound K / L-zeolite.
[Aspect 18]

Any of the aforementioned embodiments, wherein the bound zeolite base of step (a) is produced by a method comprising mixing the zeolite with a binder, extruding the mixture, drying and calcining. The method described in one.
[Aspect 19]

Aspect 1 in which the bound zeolite base of step (a) is produced by a method comprising mixing K / L-zeolites with silica, extruding the mixture, drying and calcining. The method according to any one of 12 to 12.
[Aspect 20]

The washing step contacts the bound zeolite base with, for example, an alkali metal salt and water, or any aqueous solution disclosed herein consisting essentially of, or consisting of, an alkali metal salt and deionized water. The method according to any one of the above embodiments, which comprises causing.
[Aspect 21]

Any of the aforementioned embodiments, wherein the cleaning step is performed at any cleaning temperature disclosed herein, eg, about 20 ° C to about 95 ° C, about 15 ° C to about 65 ° C, or about 30 ° C to about 50 ° C. The method described in one.
[Aspect 22]

The cleaning steps include any number of cleaning cycles (such as 1 to 4 or 2 to 8) and any cleaning cycle period (about 1 minute to about 6 hours, or about 5 minutes to about 2) disclosed herein. The method according to any one of the aforementioned embodiments, comprising (such as a time range).
[Aspect 23]

The concentration of the alkali metal in the aqueous solution is in any concentration range disclosed herein, eg, about 0.01M to about 5M, about 0.01M to about 1M, about 0.01M to about 0.45M, or The method according to any one of the aforementioned embodiments, which is from about 0.05 M to about 0.3 M.
[Aspect 24]

The ratio of the weight of the aqueous solution to the weight of the bound zeolite base is in any of the weight ratios disclosed herein, eg, about 0.4: 1 to about 10: 1, about 0.5: 1 to about. The method according to any one of the aforementioned embodiments, which is 8: 1 or about 1: 1 to about 5: 1.
[Aspect 25]

The washing step comprises the bound zeolite base, for example, from about 0.03 mol to about 1 mol, from about 0.1 mol to about 0.9 mol, or per kg of the bound zeolite base (or per kg of alkali metal enriched zeolite carrier). The method according to any one of the aforementioned embodiments, enriched with any molar amount of alkali metal disclosed herein from about 0.03 mol to about 0.7 mol.
[Aspect 26]

The alkali metal enriched zeolite carrier is based on the total weight of the alkali metal enriched zeolite carrier, and any weight percent of sodium disclosed herein, such as 0% by weight to about 0.35% by weight, 0% by weight to. Described in any one of the aforementioned embodiments, comprising about 0.3% by weight, about 0.03% by weight to about 0.35% by weight, or about 0.05% by weight to about 0.3% by weight of sodium. the method of.
[Aspect 27]

The method according to any one of the above-described embodiments, wherein step (b) is the only step of utilizing an alkali metal, for example, an alkali metal salt in the method.
[Aspect 28]

The method according to any one of the aforementioned embodiments, further comprising drying and / or calcining the alkali metal enriched zeolite carrier prior to step (c).
[Aspect 29]

The carrying catalyst is any weight percent of the transition metal disclosed herein, eg, 0.1% to about 10% by weight, about 0.2% by weight to about 5% by weight, based on the total weight of the carrying catalyst. , Or the method according to any one of the aforementioned embodiments, comprising from about 0.3% by weight to about 2% by weight of the transition metal.
[Aspect 30]

The method according to any one of the aforementioned embodiments, wherein the transition metal comprises platinum.
[Aspect 31]

The supported catalyst according to any one of the above-described embodiments, wherein the transition metal is platinum.
[Aspect 32]

The carrying catalyst is in any weight percent range of platinum disclosed herein, eg, about 0.1% to about 10% by weight, about 0.2% by weight to about 5% by weight, based on the total weight of the carrying catalyst. %, Or the method according to any one of the aforementioned embodiments, comprising from about 0.3% to about 2% by weight.
[Aspect 33]

In step (c), the alkali metal enriched zeolite carrier is subjected to tetraamine platinum (II) chloride, tetraamine platinum (II) nitrate, platinum (II) acetylacetonate, platinum (II) chloride, ammonium tetrachloroplatinate (II). , The method according to any one of the aforementioned embodiments, comprising mixing with a transition metal-containing compound comprising platinum chloride acid, platinum (II) nitrate, or a combination thereof.
[Aspect 34]

The method according to any one of the aforementioned embodiments, wherein the halogen comprises chlorine and / or fluorine.
[Aspect 35]

The method according to any one of the aforementioned embodiments, wherein step (c) comprises mixing the alkali metal enriched zeolite carrier with a chlorine-containing compound and / or a fluorine-containing compound.
[Aspect 36]

The method according to any one of aspects 1 to 35, wherein the halogen comprises chlorine.
[Aspect 37]

The carrying catalyst is any weight percent chlorine disclosed herein, eg 0.05% by weight to about 5% by weight, about 0.1% by weight to about 1.5% by weight, based on the total weight of the carrying catalyst. %, The method of aspect 36, comprising about 0.2% by weight to about 1% by weight of chlorine.
[Aspect 38]

The method according to any one of aspects 1-37, wherein the halogen comprises fluorine.
[Aspect 39]

The carrying catalyst is any weight percent of fluorine disclosed herein based on the total weight of the carrying catalyst, eg, about 0.05% by weight to about 5% by weight, about 0.1% by weight to about 1. 38. The method of aspect 38, comprising 5% by weight, about 0.2% by weight to about 1% by weight of fluorine.
[Aspect 40]

The method according to any one of the aforementioned embodiments, wherein the method further comprises drying and / or firing the supported catalyst after step (c).
[Aspect 41]

The aforementioned embodiment further comprises a reduction step after step (c), wherein the reduction step comprises contacting the carrier catalyst with any reducing gas stream disclosed herein, including, for example, hydrogen. The method described in any one of.
[Aspect 42]

41. The method of aspect 41, wherein the reduction step is performed at any reduction temperature disclosed herein, eg, in the range of about 100 ° C to about 700 ° C, or about 200 ° C to about 600 ° C.
[Aspect 43]

A carrier catalyst obtained by the method according to any one of the above embodiments, for example, a carrier aromatization catalyst.
[Aspect 44]

The carrier catalyst is any ppm amount (based on weight) disclosed herein based on the total weight of the carrier catalyst, eg, from about 10,000 ppm to about 125,000 ppm (about 1% to about 12.5% by weight). ), Approximately 20,000 ppm to approximately 100,000 ppm (approximately 2% by weight to approximately 10% by weight), or approximately 30,000 ppm to approximately 90,000 ppm (approximately 3% by weight to approximately 9% by weight) containing an alkali metal. The carrying catalyst or method according to any one of the above embodiments.
[Aspect 45]

1. Catalyst or method.
[Aspect 46]

The aforementioned embodiment, wherein the supported catalyst has a surface area of any range of the surface areas disclosed herein, eg, about 100 m ² / g to about 170 m ² / g, or about 100 m ² / g to about 150 m ² / g. The supported catalyst or method according to any one of the above.
[Aspect 47]

The alkali metal enriched zeolite carrier covers any range of surface areas disclosed herein, eg, about 120 m ² / g to about 250 m ² / g, or about 130 m ² / g to about 230 m ² / g. The carrier catalyst or method according to any one of the above-mentioned embodiments.
[Aspect 48]

Any of the aforementioned embodiments, wherein the supported catalyst has a pore volume area smaller than the pore volume area of the catalyst obtained by washing the bound zeolite base with an aqueous solution containing no alkali metal under the same catalyst production conditions. The carrier catalyst or method according to one.
[Aspect 49]

The supported catalyst may be in any range of pore volumes disclosed herein, eg, from about 0.015 cc / g to about 0.05 cc / g, or from about 0.02 cc / g to about 0.045 cc / g. The supported catalyst or method according to any one of the above-described embodiments, which has a pore volume.
[Aspect 50]

The alkali metal enriched zeolite carrier comprises any range of pore volumes disclosed herein, eg, from about 0.025 cc / g to about 0.08 cc / g, or from about 0.03 cc / g to about 0. The carrier catalyst or method according to any one of the aforementioned embodiments, which has a pore volume of 07 cc / g.
[Aspect 51]

One of the aforementioned embodiments, wherein the carrier catalyst comprises a _TEOR in any range disclosed herein, eg, from about 499 ° C. (930 ° F) to about 530 ° C. (986 ° F). The supported catalyst or method according to the description.
[Aspect 52]

The carrier catalyst is in any selectivity range disclosed herein, eg, about 0.91 to about 0.97, about 0.92 to about 0.98, about 0.92 to about 0.97, or about. The carrying catalyst or method according to any one of the aforementioned embodiments, characterized by benzene selectivity (or toluene selectivity) of 0.95 to about 0.98.
[Aspect 53]

The carrier catalyst has greater benzene selectivity (or toluene selectivity) than the catalyst obtained by washing the bound zeolite base with an alkali metal-free aqueous solution under the same catalyst production and aromatization reaction conditions. The carrying catalyst or method according to any one of the embodiments.
[Aspect 54]

The aspect of said embodiment, wherein the carrier catalyst has a platinum dispersity of any range disclosed herein, eg, about 50% to about 70%, about 50% to about 65%, or about 55% to about 70% platinum dispersity. The carrier catalyst or method according to any one.
[Aspect 55]

A reforming method comprising contacting a hydrocarbon raw material with a carrying aromatization catalyst under reforming conditions in a reactor system to produce an aromatic product, wherein the carrying aromatization catalyst is any of the above embodiments. The reforming method which is the carrying catalyst according to one.
[Aspect 56]

Any of the hydrocarbon feedstocks disclosed herein include, for example, non _- aromatic hydrocarbons, C6 _{- C9} alkanes and / or cycloalkanes, or C6 _- C8 alkanes and / or cycloalkanes. The method defined in aspect 55, which is the hydrocarbon raw material of the above.

Claims (31)

It is a method for manufacturing a supported catalyst.
(A) Prepare a bound zeolite base;
(B) The alkali metal-enriched zeolite carrier is produced by washing the bound zeolite base with an aqueous solution containing an alkali metal; and (c) the alkali metal-enriched zeolite carrier is impregnated with a transition metal and a halogen to provide a supporting catalyst. A method that involves manufacturing ,
The method described above , wherein the supported catalyst has a surface area of 100 m ² / g to 170 m ² / g. The first aspect of claim 1, wherein the alkali metal is potassium, the alkali metal-enriched zeolite carrier is a potassium-enriched zeolite carrier, and the concentration of potassium in the aqueous solution is in the range of 0.1 M to 0.45 M. the method of. The method of claim 1 or 2, wherein the method further comprises drying and / or calcining the alkali metal enriched zeolite carrier prior to step (c). The method according to any one of claims 1 to 3, wherein the surface area of the supported catalyst is determined by the BET method. The method according to any one of claims 1 to 4, wherein the carrier catalyst has a pore volume determined by the t-plot method of 0.015 cc / g to 0.05 cc / g. The method according to any one of claims 1 to 5, wherein the aqueous solution in the step (b) contains a potassium salt, preferably a potassium chloride salt. The method according to any one of claims 1 to 6, wherein the washing step comprises contacting the bound zeolite base with the aqueous solution in step (b), wherein the aqueous solution essentially comprises an alkali metal salt and deionized water. the method of. The method according to any one of claims 1 to 7, wherein the cleaning step is performed at a cleaning temperature in the range of 20 ° C to 95 ° C. The method of any one of claims 1-8, wherein the cleaning step comprises 2 to 8 cleaning cycles; and a cleaning cycle time in the range of 1 minute to 6 hours. The method according to any one of claims 1 to 9, wherein the ratio of the weight of the aqueous solution to the weight of the bound zeolite base in the step (b) is 0.4: 1 to 10: 1. The method according to any one of claims 1 to 10, wherein the washing step enriches the bound zeolite base with 0.03 mol to 1 mol of alkali metal per kg of bound zeolite base. The method according to any one of claims 1 to 11, wherein the washing step enriches the bound zeolite base with 0.03 mol to 1 mol of alkali metal per kg of alkali metal enriched zeolite carrier. The method according to any one of claims 1 to 12, wherein step (b) is the only step of utilizing potassium or a potassium salt in the method. The supported catalyst has a surface area determined by the BET method in the range of 100 m ² / g to 170 m ² / g and a pore volume determined by the t-plot method in the range of 0.015 cc / g to 0.05 cc / g. , The method according to any one of claims 1 to 13. The method according to any one of claims 1 to 14.
A method comprising the aqueous solution comprising potassium chloride; or the aqueous solution further comprising rubidium, cesium, or a combination thereof. A reforming process comprising contacting a hydrocarbon raw material with a carrier catalyst obtained by the method according to any one of claims 1 to 15 under reforming conditions in a reactor system to produce an aromatic product. .. The method according to claim 1, wherein the alkali metal is cesium, and the alkali metal-enriched zeolite carrier is a cesium-enriched zeolite carrier. 17. The method of claim 17, wherein the method further comprises drying and / or calcining the cesium-enriched zeolite carrier prior to step (c). 17. The method of claim 17 or 18, wherein the supported catalyst has a surface area determined by the BET method from 100 m ² / g to 170 m ² / g. The method according to any one of claims 17 to 19, wherein the carrier catalyst has a pore volume determined by the t-plot method of 0.015 cc / g to 0.05 cc / g. The method according to any one of claims 17 to 20, wherein the aqueous solution contains a cesium salt and, if desired, a cesium chloride salt. The method of any one of claims 17-21, wherein the washing step comprises contacting the bound zeolite base with an aqueous solution consisting essentially of a cesium salt and deionized water. The method according to any one of claims 17 to 22, wherein the cleaning step is performed at a cleaning temperature in the range of 20 ° C to 95 ° C. The method of any one of claims 17-23, wherein the cleaning step comprises 2 to 8 cleaning cycles; and a cleaning cycle time in the range of 1 minute to 6 hours. The method according to any one of claims 17 to 24, wherein the ratio of the weight of the aqueous solution to the weight of the bound zeolite base is 0.4: 1 to 10: 1. 25. One of claims 17-25, wherein the washing step enriches the bound zeolite base with 0.03 mol to 1 mol of cesium per kg of bound zeolite base or 1 kg of alkali metal enriched zeolite carrier. the method of. The method according to any one of claims 17 to 26, wherein step (b) is the only step of utilizing cesium or a cesium salt in the method. The method according to any one of claims 17 to 27, wherein the concentration of cesium in the aqueous solution is in the range of 0.01 M to 5 M. The aqueous solution further comprises potassium, rubidium, or a combination thereof.
The carrier catalyst comprises 5% to 30% by weight of the binder based on the total weight of the carrier catalyst.
The method according to any one of claims 17 to 28. The method according to any one of claims 17 to 19, wherein the carrier catalyst is based on the total weight of the carrier catalyst.
With 0.2% by weight to 5% by weight of transition metals;
With 0.2% by weight to 3% by weight of halogen;
A method comprising 2% by weight to 10% by weight of cesium. A reforming process comprising contacting a hydrocarbon raw material with a carrier catalyst obtained by the method according to any one of claims 17 to 30 under reforming conditions in a reactor system to produce an aromatic product. ..

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